Non-black EPDM roof membranes with improved weathering

ABSTRACT

A non-black roofing membrane comprises an EPDM rubber; a non-black filler; a UV light stabilizer selected from the group consisting of NOR-HALS of the formula 
                         
wherein R* is C 1 -C 20 alkyl, OH-substituted C 1 -C 20 alkyl, optionally C 1 -C 4  alkyl-substituted C 5 -C 12 cycloalkyl, C 7 -C 9 phenylalkyl or O- or S-interrupted C 2 -C 20 alkyl, preferably C 1 -C 12 alkyl, benzyl or C 5 -C 8  cycloalkyl especially C 6 -C 10 alkyl or cyclohexyl; and a cure package. The resultant roofing membrane provides increased weathering resistance.

This application is a continuation of U.S. Ser. No. 12/982,198 filed onDec. 30, 2010, now abandoned, which is a Non-Provisional Application ofU.S. Provisional Application Ser. No. 61/291,579, filed on Dec. 31,2009, both of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention generally relates to sheeting material used forapplications such as roofing. More particularly, the present inventionrelates to non-black, sulfur-cured EPDM sheeting material of the typethat is devoid of black pigments or carbon black. Specifically, thepresent invention relates to an EPDM sheeting material having a UV lightstabilizer that does not become deactivated upon thermal orphoto-oxidation, or upon the rubber's mixing and curing processes. Amethod is also provided for covering the roofs of buildings whichincludes the step of employing the sheeting material of the presentinvention.

BACKGROUND OF THE INVENTION

Ethylene-propylene-diene terpolymer (EPDM) is extensively used in avariety of applications. For example, it is particularly useful as apolymeric sheeting material, which, because of its excellent physicalproperties, flexibility, weathering resistance, low temperatureproperties and heat aging resistance, has gained acceptance as a roofingmembrane for covering industrial and commercial roofs. These roofingmembranes are typically applied to the roof surface in a vulcanized orcured state and serve as an effective barrier to prevent the penetrationof moisture to the covered roof.

Traditional EPDM roofing membranes are generally black or very dark incolor, and are typically prepared by compounding the base polymer ofEPDM with one or more carbon black fillers, processing oil, and otherdesired ingredients such as plasticizers, antidegradants,adhesive-enhancing promoters, etc., in a suitable mixer, and calenderingthe resulting compound into the desired thickness. The roofing membranemay also be cured by vulcanizing the resultant sheet in the presence ofone or more vulcanizing agents and/or compatible vulcanizingaccelerators. Vulcanizing agents such as sulfur or sulfur-donatingcompounds such as mercaptans are typically used, although vulcanizationand curing may be done using other agents or in the presence of othercompounds.

While black or dark-colored EPDM membranes have been used for decades ascommercial single-ply roofing membranes, such membranes are known toabsorb sunlight and become hot. This has lead to various environmentaland energy concerns. In recent years, great efforts have been madetoward producing white and/or other non-black membranes, including notonly EPDM membranes but also thermoplastic olefin (TPO) membranes, thatare more environmentally friendly and more energy efficient. Variousmineral fillers such as clay, talc, silicas, mica, calcium carbonate,and the like, either individually or in various combinations, have beenadded to various roofing membrane formulations to improve energyabsorption characteristics.

Because non-black or light colored membranes do not have black pigmentsor carbon black in them to absorb UV light, UV stabilizers have beenneeded in the membranes to prevent the polymers from degrading in thesunlight. UV light stabilizers have been used in various TPOformulations (TPO is a thermoplastic material) where the formulationsare to be used in membranes for outdoor use. For instance, a typical UVlight stabilizer for plastic products, including TPO membranes, is ahindered amine light stabilizer, also referred to as HALS. HALS acts asa radical scavenger. Through the formation of nitroxyl radicals,hindered amines terminate and deactivate any alkyl radicals and/orperoxide radicals that may participate in the photo-oxidation process.

Unfortunately, due to the strong basic nature of the hindered amines,HALS cannot be used in thermoplastic roof membranes that are acidic innature, such as polyvinyl chloride (PVC) membranes. It is well knownthat PVC releases hydrochloric acid (HCl) upon thermal andphoto-oxidation. It is believed that the HCl combines with HALS andobstructs the stabilizer's ability to form nitroxyl radicals, therebyimpairing the scavenger ability of the HALS. It is further believed thatmembranes containing EPDM rubber in their formulations could not useHALS due to similar, but not identical, reasons as those above. It isbelieved that HALS reacts with one or more ingredients, e.g., a filler,a curative, the EPDM rubber, during the rubber mixing and/or curingprocesses, the reaction causing the HALS to not form the necessarynitroxyl radicals, due at least in part to the high-temperature reactiveenvironment.

Nevertheless, the use of HALS as a radical scavenger and UV lightstabilizer would be beneficial in non-black EPDM membranes, if it wouldnot be deactivated by acids or by the high-temperature processes asrequired in the production of EPDM membranes. Thus, the need exists fora HALS-based UV light stabilizer suitable for use in a non-black EPDMmembrane and, more specifically in one embodiment, a sulfur-cured EPDMmembrane.

SUMMARY OF THE INVENTION

One or more embodiments of the present invention provide a non-blackroofing membrane comprising an EPDM rubber; from about 10 parts to about300 parts by weight of a non-black filler per 100 parts by weightrubber; from about 0.1 parts to about 10 parts by weight of a UV lightstabilizer selected from the group consisting of NOR-HALS; and a curepackage. In one or more embodiments, the non-black roofing membrane maybe a single-ply membrane. In one or more embodiments, the non-black EPDMroofing membrane with the NOR-HALS stabilizer has effective UV lightstability when measured by a Xenon Arc weathering test. In one or moreembodiments, the non-black roofing membrane with the NOR-HALS stabilizerhas much less cracking and damage due to exposure for 10,000 hours inthe Xenon Arc weathering test, than does a comparable membrane that doesnot include the NOR-HALS stabilizer.

One or more embodiments of the present invention further provide amethod for the production of a non-black roofing membrane comprisingmixing an EPDM rubber, a non-black filler, and a UV stabilizercontaining a NOR-HALS stabilizer in a masterbatch to form an uncuredcompound, calendering the uncured compound into one or more layers toform a sheet, and curing the calendered uncured compound such that theEPDM rubber has improved resistance to UV light as compared to an EPDMmembrane made comparably, but without the NOR-HALS stabilizer.

One or more embodiments of the present invention still further provide alaminate membrane comprising a non-black first layer including the curedEPDM rubber, non-black filler and NOR-HALS UV light stabilizer asdescribed above; and a second layer including cured elastomeric olefiniccopolymer and carbon black, and optionally, a scrim fabric.

DETAILED DESCRIPTION OF AN EMBODIMENT OF THE INVENTION

At least one representative embodiment of the present invention isdirected toward a non-black roofing membrane or sheeting material thatincludes a EPDM rubber; one or more non-black reinforcing fillers (e.g.,silica, clay, talc, mica, calcium carbonate); and a UV light stabilizerselected from a group of hindered amine light stabilizers known asNOR-HALS. Prior non-black EPDM roof sheeting materials were devoid ofany UV light stabilizers that contained hindered amines, primarilybecause mixing and processing and curing temperatures for the productionof the masterbatch of the ingredients are so high that the HALSstabilizer would react with one or more of the other ingredient and,hence, obstruct the stabilizer's ability to form nitroxyl radicals.

In addition, even if it were possible to blend a hindered amine lightstabilizer (HALS) into the masterbatch at reasonable temperatures so asnot to destroy the stabilizer's ability to form nitroxyl radicals, thecuring process for producing a vulcanized EPDM rubber roofing membraneor sheeting material requires a temperature that would have, heretofore,obstructed the formation of nitroxyl radicals by the stabilizer duringthe curing process. Thus, prior to this invention, no hindered amineswere capable of forming nitroxyl radicals during the mixing and curingprocesses required for the production of EPDM roofing membranes orsheeting material. For instance, EPDM rubber roofing membranes aretypically cured at a high temperature, on the order of about 300° F.(about 160° C.) or more, for a relatively short period of time, on theorder of less than one hour, e.g., about 45 minutes, or at lowertemperatures, on the order of about 280° F. or less, for a relativelylong period of time, on the order of 3 hours or more. In curing the EPDMrubber membrane, it has been found that hindered amines other than theNOR-HALS interfere with the curing process by affecting the crosslinkingof the rubber. This problem is not present with PVC plastic, as PVCwould melt at such temperatures.

In the present invention, a new group of hindered amines have been foundthat will not be become deactivated by the mixing and curing processesassociated with the production of EPDM membranes or sheeting material.These UV stabilizers, heretofore, were found not to become deactivatedby acids such as HCl. Thus, this new group of hindered amines has beenshown to be suitable for use in the production of cured plastic articlesmade of PVC, as noted in the Journal of Vinyl & Additive Technology2005, in an article entitled “A Radically New UV Stabilizer for FlexiblePVC Roofing Membranes” by Gerald Capocci et al., the disclosure of whichis incorporated herein by reference. These new types of hindered amines(HALS) provide for an O—R group to attach to the hindered amine, and areknown in the industry as NOR-HALS. Thus, they are not strong bases and,as such, do not become deactivated by acids. It has now been found thatthe NOR-HALS can survive the harsh EPDM mixing and curing processes, andother high-temperature reactive environments, to provide a non-blackfilled EPDM membrane with improved UV stabilization or improvedweathering resistance. Suitable examples include a proprietary compoundsold under the trademark Tinuvin XT 833™ by Ciba Geigy.

In one or more embodiments, a vulcanizable composition including notonly a vulcanizable EPDM polymer and a non-black reinforcing filler, butalso a UV stabilizer selected from the group consisting of NOR-HALS isprovided. An uncured rubber sheet can be formed from this compositionand cured such that, upon curing, the UV stabilizer remains unobstructedin its formation of nitroxyl radicals and is free to act as a radicalscavenger. In one or more embodiments, the NOR-HALS act to reduce theaffects of UV light, via thermal- and photo-oxidation, on the non-blackfilled EPDM membranes, so as to provide advantageous weatheringresistance properties to the composition.

In one or more embodiments, the EPDM membranes of the present inventionare monolithic membranes. These membranes include those where thecomposition of the membrane (excluding any optional scrim) ishomogeneous throughout the thickness of the membrane. In one or moreembodiments, these monolithic membranes derive from a single calenderedsheet. In one or more embodiments, these monolithic membranes mayoptionally include a scrim such as a reinforcing scrim. Membranesincluding a scrim fabric may be referred to as composite membranes.

In other embodiments, the membranes of the present invention arelaminate membranes including at least one non-black layer prepared froma non-black rubber formulation as described herein. In one or moreembodiments, these laminate membranes include at least one layerincluding carbon black as a filler. In certain embodiments, thesebi-laminate membranes may be composites and include scrim.

In either event, the membranes of the present invention include at leastone non-black polymeric layer that derives from the non-blackvulcanizable compositions described herein. The membranes of the presentinvention (or at least one non-black layer of the membranes of thepresent invention) are prepared from non-black vulcanizable compositionsof matter that include an EPDM rubber, a non-black reinforcing filler, acurative, and a UV stabilizer. They may be simply referred to asvulcanizable compositions. Optional ingredients may also be added.

In one or more embodiments, useful rubber includes elastomeric olefiniccopolymer rubber, which may simply be referred to as olefinic rubber,olefinic copolymer, or simply rubber. In one or more embodiments, usefulolefinic rubber includes rubber that is capable of being cured orcrosslinked with sulfur or sulfur-based cure systems.

In one or more embodiments, the olefinic copolymer is a terpolyer thatincludes mer units that derive from ethylene, α-olefin, and optionallydiene monomer. Useful α-olefins include propylene. In one or moreembodiments, the diene monomer may include dicyclopentadiene,alkyldicyclopentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,1,4-heptadiene, 2-methyl-1,5-hexadiene, cyclooctadiene, 1,4-octadiene,1,7-octadiene, 5-ethylidene-2-norbornene, 5-n-propylidene-2-norbornene,5-(2-methyl-2-butenyl)-2-norbornene, and mixtures thereof. Olefinicterpolymers and methods for their manufacture are known as disclosed atU.S. Pat. No. 3,280,082, which is incorporated herein by reference. Forpurposes of this specification, elastomeric olefinic copolymers may bereferred to as elastomeric olefinic terpolymers, terpolymers, or simplyEPDM.

In one or more embodiments, the terpolymer may include at least 55weight percent, in other embodiments at least 60 weight percent, inother embodiments at least 62 weight percent, and in other embodimentsat least 64 weight percent mer units deriving from ethylene; in these orother embodiments, the elastomeric terpolymer may include less thanabout 73 weight percent, in other embodiments less than about 70 weightpercent, and in other embodiments less than about 69 weight percent, merunits deriving from ethylene.

In one or more embodiments, the elastomeric terpolymer may include atleast 1 percent by weight, in other embodiments at least 1.5 percent byweight, in other embodiments at least 2 weight percent, in otherembodiments at least 2.4 weight percent, mer units deriving from dienemonomer; in these or other embodiments, the elastomeric terpolymer mayinclude less than about 4 weight percent, and in other embodiments lessthan about 3.2 weight percent, mer units deriving from diene monomer. Inone or more embodiments, the balance of the mer units derive frompropylene or other α-olefins. In particular embodiments of the presentinvention, the use of a silane coupling agent may advantageously providefor the use of terpolymer rubber having relatively low amounts of diene;for example, terpolymer rubber including from about 1 to about 2percent, or in other embodiments from about 1.3 to about 1.7 percent,mer units deriving from diene monomer may be used.

In one or more embodiments, the useful elastomeric olefinic terpolymer(EPDM) may be characterized by a Mooney Viscosity (ML₁₊₄@125° C.) ofabout 35 to about 70, and in other embodiments from about 50 to about70.

Useful EPDM varieties are commercially available. Examples includeRoyalene® 512, which has a Mooney Viscosity (ML₁₊₄@125° C.) range of 52to 67, and an ethylene to propylene ratio of 68/32. Other example EPDMssuitable for the present invention include, but are not limited to,Royalene® 4569 and Royalene® 502.

In one or more embodiments, the EPDM membrane is cured or crosslinked.In one or more embodiments, the EPDM membrane is cured at a temperatureof at least about 150° C.; in another embodiment, at least about 160°C.; and in another embodiment at least about 170° C. In anotherembodiment, the EPDM membrane may be cured in an autoclave in thepresence of steam and pressure. In yet another embodiment, the EPDMmembrane may be cured at a temperature of less than about 150° C., butthe EPDM membrane curing process will extend at least 3 hours or more,not less than one hour as in the other embodiments noted above.

EPDM can be cured by using numerous techniques such as those that employsulfur cure systems, peroxide cure systems, and quinone-type curesystems. The sulfur cure systems may be employed in combination withvulcanizing accelerators. Useful accelerators include thioureas such asethylene thiourea, N,N-dibutylthiourea, N,N-diethylthiourea and thelike; thiuram monosulfides and disulfides such as tetramethylthiurammonosulfide (TMTMS), tetrabutylthiuram disulfide (TBTDS),tetramethylthiuram disulfide (TMTDS), tetraethylthiuram monosulfide(TETMS), dipentamethylenethiuram hexasulfide (DPTH) and the like;benzothiazole sulfenamides such as N-oxydiethylene-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide,N,N-diisopropyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzothiazolesulfenamide (TBBS) (available as Delac® NS from Chemtura, Middlebury,Conn.) and the like; other thiazole accelerators such as2-mercaptobenzothiazole (MBT), benzothiazyl disulfide (MBTS),N,N-diphenylguanidine, N,N-di-(2-methylphenyl)-guanidine,2-(morpholinodithio)benzothiazole disulfide, zinc2-mercaptobenzothiazole and the like; dithiocarbamates such as telluriumdiethyldithiocarbamate, copper dimethyldithiocarbamate, bismuthdimethyldithiocarbamate, cadmium diethyldithiocarbamate, leaddimethyldithiocarbamate, sodium butyldithiocarbamate, zincdiethyldithiocarbamate, zinc dimethyldithiocarbamate, zincdibutyldithiocarbamate (ZDBDC) and mixtures thereof. Sulfur donor-typeaccelerators (e.g. di-morpholino disulfide and alkyl phenol disulfide)may be used in place of elemental sulfur or in conjunction withelemental sulfur if desired.

Examples of suitable peroxides that can be used as curing agents orco-curing agents include alpha-cumyl hydroperoxide, methylethylketoneperoxide, hydrogen peroxide, acetylacetone peroxide, t-butylhydroperoxide, t-butyl peroxybenzoate, 2,5-bis(t-butylperoxy)-2,5-dimethylhexene, lauryl peroxide, benzoyl peroxide,2,4-dichlorobenzoyl peroxide, dibenzoyl peroxide,bis(p-monomethylene-benzoyl) peroxide, bis(p-nitrobenzoyl) peroxide,phenylacetyl peroxide, and mixtures thereof.

Examples of inorganic peroxides which can be used as co-curing agentswith p-quinone dioxime include lead peroxide, zinc peroxide, bariumperoxide, copper peroxide, potassium peroxide, silver peroxide, sodiumperoxide, calcium peroxide, metallic peroxyborates, peroxychromates,peroxydicarbonates, peroxydiphosphates, peroxydisulfates,peroxygermanates, peroxymolybdates, peroxynitrates, magnesium peroxide,sodium pyrophosphate peroxide, and mixtures thereof.

Examples of polysulfide activators for the quinone-type co-curing agentsinclude calcium polysulfide, sodium polysulfide, as well as organicpolysulfides having the general formula R—(S)_(x)—R, wherein R is ahydrocarbon group and x is a number from 2-4. Examples of organicpolysulfides are disclosed in U.S. Pat. No. 2,619,481, which isincorporated herein by reference.

Conventional radiation equipment and techniques can optionally beemployed in the practice of this invention. Suitable ionizingcrosslinking promoters that can be used include: liquid high-vinyl1,2-polybutadiene resins containing 90 percent 1,2-vinyl content;Sartomer SR-206 (ethylene glycol dimethacrylate), Di-Cup R(dicumylperoxide, about 98 percent active), and Pental A (pentaerythritol resinprepared from tall oil). These chemical additives are preferablycompatible with the other ingredients in the composition; they may alsofunction to reduce the dosage of ionizing radiation needed to obtain thedesired level of crosslinking.

Sulfur and sulfur-containing cure systems may be used, and may also beused with an accelerator. Suitable amounts of sulfur can be readilydetermined by those skilled in the art. In one or more embodimentsroughly about 1 part by weight (pbw) sulfur per 100 parts by weightrubber (phr) may be used. The amount of accelerator can also be readilydetermined by those skilled in the art.

In one or more embodiments, non-black reinforcing fillers includemineral fillers that are characterized by a particle size (averagediameter or cross-section) of less than 10 microns, in other embodimentsless than 5 microns, and in other embodiments less than 1 micron. Inthese or other embodiments, these fillers are characterized by aparticle size of at least 10 nanometers, in other embodiments at least50 nanometers, and in other embodiments at least 100 nanometers.Suitable amounts of non-black reinforcing fillers may include from 0parts by weight (pbw) per 100 parts by weight rubber (phr) to 300 partsby weight (pbw) per 100 parts by weight rubber (phr). In anotherembodiment, the amounts may range from 10 parts to 150 parts by weightphr, and in another embodiment, from 40 parts to 100 parts by weightphr.

In one or more embodiments, one or more non-black reinforcing fillersinclude a moiety or group that is capable of providing a non-black colorto an EPDM sheeting material or roofing membrane. In one or moreembodiments, the non-black reinforcing filler will be chemically orphysically compatible with the NOR-HALS. In one or more embodiments, theEPDM membrane is devoid of any carbon black fillers. In one or moreother embodiments, the EPDM membrane is devoid of any fillers, otherthan specified UV stabilizers, that absorb UV light. In otherembodiments, the EPDM membrane may be devoid of petroleum-derivedfillers.

In one or more embodiments, a single type of reinforcing non-blackfiller may be employed, and in other embodiments two or more reinforcingnon-black fillers may be used in conjunction. In one or moreembodiments, one or more reinforcing fillers may be employed inconjunction with one or more non-reinforcing fillers. Thenon-reinforcing fillers may include non-black mineral fillers that donot include groups or moieties that will react with a silane and/or arelarger in particle size than the reinforcing fillers.

In one or more embodiments, silica is employed as the non-blackreinforcing filler. In one or more embodiments, silica filler isemployed alone. In other embodiments, silica filler is included withTiO₂. In other embodiments, silica filler is included along with othermineral fillers that do not substantially reinforce the composition.

In one or more embodiments, useful forms of silica (silicon dioxide)include crystalline and amorphous silica. The crystalline form of silicaincludes quartz, tridymite and cristobalite. Amorphous silica may occurwhen the silicon and oxygen atoms are arranged in an irregular form asidentified by X-ray diffraction. In one or more embodiments, the silicais a precipitated silica. In these or other embodiments, fumed silica isemployed.

Commercially available forms are available from PPG Industries, Inc.(Monroeville, Pa.), Degussa Corporation (Parsippany, N.J.) and J.M.Huber Corporation (Atlanta, Ga.). One useful commercial product isRubbersil® RS-150D, which is characterized by a BET surface area of 150m²/g, tapped density of 230 g/liter, pH (5% in water suspension) of 7,SiO2 content of 98%, Na2SO4 content of 2%, and Al2O3 content of 0.2%. Inat least one embodiment, silica filler may be used without any othermineral fillers.

In one or more embodiments, other non-black reinforcing fillers includemagnesium hydroxide. In yet other embodiments, non-black reinforcingfillers include aluminum trihydrate.

In one or more embodiments, titanium dioxides may be optionallyincluded. Useful titanium dioxides include rutile forms of titaniumdioxide. One useful commercial product is TiPure® R-960 (DuPont), whichis a fine, white powder having a specific gravity of 3.90. Anothersuitable titanium dioxide product is CR-800 (TRONOX), which is believedto be characterized by a titanium dioxide content of about 96% and aspecific gravity of about 3.8 to about 4.1.

In one or more embodiments, talc may optionally be included. Useful talcincludes hydrated magnesium silicate. In one or more embodiments, talccan be represented by the formulae Mg₃Si₄O₁₀(OH)₂ or 3MgO.4SiO₂.H₂O.Exemplary forms of talc include talcum, soapstone, steatite, cerolite,magnesium talc, steatite-massive, and mixtures thereof. Talc filler maycontain various other minerals such as dolomite, chlorite, quartz, andthe like. Talc used as filler may also exhibit characteristics such ashydrophobicity, organophilicity, non-polarity, and chemically inertness.A representative commercially available talc is Talc 9107, which isavailable from Polar Minerals (Mt. Vernon, Ind.), which is non-abrasive,chemically inert, has a specific gravity of about 2.8, a pH of about8.7, a refractive index of about 1.57 at 23° C., and a moisture contentof less than about 0.3 weight percent.

Further suitable talc is Mistron® Vapor Talc, which is available fromLuzenac America (Centennial, Colo.). Mistron® Vapor Talc is a soft,ultra-fine, white platy powder having a specific gravity of 2.75, amedian particle size of 1.7 microns, an average surface area of 18 m²/g,and a bulk density (tapped) of 20 lbs/ft³. Other talcs commerciallyavailable from Luzenac America (Centennial, Colo.), include Vertal MB,and Silverline 002. In one embodiment, talc is characterized as a platy,chemically inert filler having a specific gravity of from about 2.6 toabout 2.8, a pH of about 7, and a moisture content of less than about0.5 weight percent.

While, in one or more embodiments, clays may be used, in otherembodiments, the present invention is devoid of the use of clays of alltypes. Where clays are used, useful clays include hydrated aluminumsilicates. In one or more embodiments, useful clays can be representedby the formula Al₂O₃SiO₂.XH₂O. Exemplary forms of clay includekaolinite, montmorillonite, atapulgite, illite, bentonite, halloysite,and mixtures thereof. In one embodiment, the clay is represented by theformula Al₂O₃SiO₂.3H₂O. In another embodiment, the clay is representedby the formula Al₂O₃SiO₂.2H₂O. In a preferred embodiment, the clay has apH of about 7.0.

In one or more embodiments, various forms or grades of clays may beemployed. Exemplary forms or grades of clay include air-floated clays,water-washed clays, calcined clays, and chemically modified (surfacetreated) clays. In other embodiments, untreated clays may be used.

Air-floated clays include hard and soft clays. In one or moreembodiments, hard clays include those characterized as having a lowermedian particle size distribution, and higher surface area than softclays. In one or more embodiments, soft clays include thosecharacterized by having a higher median particle size distribution andlower surface area than hard clays. Hard and soft clays are disclosed inU.S. Pat. Nos. 5,468,550, and 5,854,327, which are incorporated hereinby reference.

In one embodiment, the air-floated clays used have a pH of from about4.0 to about 8.0, and in another embodiment, the pH is about neutral.Useful airfloated clays have an average particle size of less than about2 microns. Typical airfloated clays have a specific gravity of around2.6 g/cc.

Airfloated clays, both hard and soft, are available through varioussources. Available from Unimin Corporation (New Canaan, Conn.) isSnobrite™ AF, which is an airfloated hard clay having a pH of about 5.5to 7.5, a median particle size of about 1 micron, and a specific gravityof about 2.6 g/cc. Available from Kentucky-Tennessee Clay Company(Mayfield, Ky.) is Paragon, which has a pH of about 4.5 to 5.5, a medianparticle size of about 1 micron, and a specific gravity of about 2.6g/cc, and Tennessee Clay No. 6, an airfloated hard clay with a pH offrom about 5.5 to 6.5, a median particle size of about 1.0 micron, and aspecific gravity of about 2.6. A soft airfloated clay from UniminCorporation (New Canaan, Conn.) is Hi White R®, which has a pH of about6.25, a median particle size of less than about 1 micron, and a specificgravity of about 2.6 g/cc, Alumex, and Suprex, all airfloated softclays. Available from J.M. Huber Corporation (Atlanta, Ga.) is Barden R,and LGB, which are both airfloated hard clays, and K-78, an airfloatedsoft clay. Available from R.T. Vanderbilt Company (Norwalk, Conn.) isMcNamee Clay, which is an airfloated soft clay having a pH of about 5.0to 7.5, a median particle size of about 1 micron and a specific gravityof about 2.6 g/cc.

Water washed clays include those clays that are more closely controlledfor particle size by the water fractionation process. This processpermits the production of clays within controlled particle size ranges.In one embodiment, the average particle size of the clay is less thanabout 2 microns in diameter. In another embodiment, the pH of the clayis about 7. Available from J.M. Huber Corporation (Atlanta, Ga.) arewater washed clays such as Polyfil® DL, Polyfil® F, Polyfil® FB,Polyfil® HG-90, Polyfil® K and Polyfil® XB. In one embodiment, a waterwashed kaolin clay includes hydrated aluminum silicate, which has a pHof from about 6 to about 7.5, and a specific gravity of about 2.6 g/cc.

Calcined clays include those that result from the removal of watercontained in clays (clays typically contain about 14% water) bycalcination. The amount of bound water removed determines the degree ofcalcination. In one embodiment, the average particle size of the clay isless than about 2 microns in diameter. In another embodiment, the pH ofthe clay is about 7. Available from J.M. Huber Corporation (Atlanta,Ga.) are calcined clays such as Polyfil® 40, Polyfil® 70, and Polyfil®80.

Chemically modified (surface treated) clays include those that havecross-linking ability, which can be imparted to the clay by modifyingthe surface of individual particles with a polyfunctional silanecoupling agent. In one embodiment, the average particle size of the clayis less than about 2 microns in diameter. In another embodiment, the pHof the clay is about 7. Available from J.M. Huber Corporation (Atlanta,Ga.) are Nucap® 100 G, Nucap® 200, Nucap® 190, Nucap® 290, Nulok® 321,Nulok® 390, and Polyfil® 368.

In one or more embodiments, UV stabilizers include those compounds knownas NOR-HALS. NOR-HALS are considered alkoxyamine hindered aminestabilizers and operate in a similar manner to hindered amine lightstabilizer (HALS), but have an O—R group attached to the hindered amine.NOR-HALS, like HALS, have the ability to scavenge radicals which areproduced by weathering. This ability may be explained by the formationof nitroxyl radicals through a process known as the Denisov Cycle. Thenitroxyl radical(R—O.) combines with free radical in polymers:R—O.+R′.→R—O—R′Although they are traditionally considered as light stabilizers, it canalso stabilize thermal degradation. NOR-HALS are not a strong base andare not deactivated by HCl.

Because the EPDM membranes and sheeting materials do not include blackfillers, UV light is not absorbed into the membranes or materials.However, if UV stabilizers were not present, UV light woulddeleteriously affect the membranes. UV stabilizers are used to preventthe various effects of UV light, such as oxidation, chain scission anduncontrolled re-combinations and cross-linking reactions. These problemsmay be caused by photo-oxidation of polymers. Polymers are considered toget weathered due to the direct or indirect impact of heat andultraviolet light. The effectiveness of the stabilizers againstweathering may depend on the solubility, ability to stabilize indifferent polymer matrix, the distribution in the matrix, evaporationloss during process and the end use.

The NOR-HALS compounds in accordance with the present invention may bederivatives of polyalkylpiperidines which comprise at least one group ofthe formula

in which G is hydrogen or methyl and G₁ and G₂ are hydrogen, methyl ortogether are ═O; the polyalkylpiperidine groups of the formula I or IIare preferably substituted in position 4 by one or two polarsubstituents or a polar spiro ring system

Useful examples of such compounds have been disclosed in U.S. Pat. Nos.4,590,231, 5,300,647, 4,831,134, 5,204,473, 5,004,770, 5,096,950,5,021,478, 5,118,736, 5,021,480, 5,015,683, 5,021,481, 5,019,613,5,021,486, 5,021,483, 5,145,893, 5,286,865, 5,359,069, 4,983,737,5,047,489, 5,077,340, 5,021,577, 5,189,086, 5,015,682, 5,015,678,5,051,511, 5,140,081, 5,204,422, 5,026,750, 5,185,448, 5,180,829,5,262,538, 5,371,125, 5,216,156, and 5,300,544, the disclosures of whichare incorporated herein by reference.

In one or more embodiments, NOR-HALS compounds may include thosecompositions of the group of the formula

in which G is hydrogen, G₁and G₂ are as defined above and G¹¹ isC₁-C₁₈alkyl, C₂-C₁₈alkenyl, C₃-C₁₈alkynyl, C₅-C₁₂cycloalkyl,C₆-C₁₀bicycloalkyl, C₅-C₈cycloalkenyl, phenyl, naphthyl,C₇-C₁₂phenylalkyl, phenyl or phenylalkyl substituted by alkyl or phenylhaving 7 to 14 carbon atoms, or is a group of the formula —CO-D′ inwhich D′ has the definitions C₁-C₁₈alkyl, C₁-C₁₈alkoxy, phenyl, orphenyl substituted by hydroxy, C₁-C₁₈alkyl, C₁-C₁₈alkoxy, amino or aminomono- or disubstituted by C₁-C₁₈alkyl or phenyl. In one or moreembodiments, G¹¹ may be C₁-C₁₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl,C₅-C₈cycloalkyl, C₇-C₉phenylalkyl, C₂-C₁₈alkanoyl, C₃-C₆alkenoyl, e.g.,C₁-C₁₈alkyl, C₅-C₈cycloalkyl or C₇-C₉phenylalkyl.

In one or more embodiments, NOR-HALS may be defined as comprising thefollowing compounds, the formula of which is

R* in this formula is C₁-C₂₀alkyl, OH-substituted C₁-C₂₀alkyl,optionally C₁-C₄ alkyl-substituted C₅-C₁₂cycloalkyl, C₇-C₉phenylalkyl orO- or S-interrupted C₂-C₂₀alkyl, preferably C₁-C₁₂alkyl, benzyl or C₅-C₈cycloalkyl especially C₆-C₁₀alkyl or cyclohexyl.

In one or more embodiments, the use of alkoxyamine hindered amines(NOR-HALS) provides for several advantages. For example, the processingproperties and the physical properties of the resultant compound have,in certain embodiments, proven to be advantageous. For example, cured,white (or non-black), filled EPDM membranes have been shown to haveincreased weathering resistance properties, based upon ASTM D4637 ascompared to cured, white (or non-black), filled EPDM membranes that didnot include the NOR-HALS. Thus, for the first time, a new UV radicalscavenger can be used in cured, non-black EPDM membranes.

In one or more embodiments, the NOR—HALS compounds are presentjudiciously to the extent of from 0.01 to 10.0 parts for example to theextent of from 0.05 to 5.0 parts. In other embodiments, they may bepresent to the extent of from 0.05 to 3.0 parts, but in particular tothe extent of from 0.1 to 2.0% by weight. The weight percentages arebased on the total amount of these compounds. The basis for calculationin this context is the total weight of the polymer excluding theNOR—HALS compounds.

Further discussion of the NOR—HALS compounds is set forth in U.S. Pat.No. 6,133,414, the disclosure of which is incorporated herein byreference.

In addition to the foregoing ingredients, the vulcanizable compositionsof this invention may also optionally include processing oils, mica,calcium carbonate, homogenizing agents, flame retardants, zinc oxide,stearic acid, and mixtures thereof. Certain embodiments may besubstantially devoid of any of these constituents.

Processing oils may be used in the present invention. Useful processingoils include paraffinic, naphthenic oils, and mixtures thereof. Theseoils may be halogenated as disclosed in U.S. Pat. No. 6,632,509, whichis incorporated herein by reference. In one or more embodiments, usefulprocessing oils are generally characterized by low sulfur content, lowaromaticity, low volatility, and a flash point of more than about 550°F. In one or more embodiments, these processing oils may be referred toas white oils. In one or more embodiments, useful oils have a sulfurcontent of less than 0.5 weight percent, in other embodiments, less than0.1 weight percent, in other embodiments less than 0.05 weight percent,and in other embodiments less than 0.01 weight percent sulfur. In one ormore embodiments, useful oils have limited unsaturation. In particularembodiments, useful oils have an unsaturation level of less than 3%, inother embodiments less than 1%, in other embodiments less than 0.5%, andin other embodiments less than 0.1%. Useful oils are commerciallyavailable. A useful oil is available under the tradename FHR Ultra 1199.

Mica includes mixtures of sodium and potassium aluminum silicate. Micacan be defined by the chemical formula αΔ2-3(Ω)4O10(Σ)2, where the α ionis potassium, sodium, barium, calcium, cesium, and/or ammonium, the Δion is aluminum, lithium, iron, zinc, chromium, vanadium, titanium,manganese, and/or magnesium, the Ω ion is silicon, aluminum, beryllium,boron, and/or iron (+3), and Σ is oxygen, fluorine, or hydroxide ion.Micas include true micas, brittle micas, and interlayer-deficient micas.True micas include a majority of singularly charged ions (e.g.,potassium and sodium) in the α position. Brittle micas include amajority of doubly charged ions (e.g., calcium or barium) in the αposition. Interlayer-deficient micas include fewer cations in theinterlayer (the layer between the tetrahedral-octahedral-tetrahedrallayers of the crystalline structure) than true or brittle micas.

Examples of true micas include aluminoceladonite (potassium aluminummagnesium iron silicate hydroxide), boromuscovite (potassiumboro-silicate hydroxide), celadonite (potassium iron magnesium silicatehydroxide), chromphyllite (potassium chromium aluminum silicatehydroxide fluoride), ferro-aluminoceladonite (potassium aluminum ironmagnesium silicate hydroxide), ferroceladonite (potassium iron magnesiumsilicate hydroxide), muscovite (potassium aluminum silicate hydroxide),nanpingite (cesium aluminum silicate hydroxide), paragonite (sodiumaluminum silicate hydroxide), roscoelite (potassium vanadium aluminumsilicate hydroxide), tobelite (ammonium aluminum silicate hydroxide),annite (potassium iron aluminum silicate hydroxide), aspidolite (sodiummagnesium aluminum silicate hydroxide), biotite (potassium magnesiumiron aluminum silicate hydroxide fluoride), eastonite (potassiummagnesium aluminum silicate hydroxide), ephesite (sodium lithiumaluminum silicate hydroxide), hendricksite (potassium zinc aluminumsilicate hydroxide), lepidolite (potassium lithium aluminum silicatefluoride hydroxide), masutomilite (potassium lithium aluminum manganesesilicate fluoride), montdorite (potassium iron manganese magnesiumaluminum silicate fluoride), norrishite (potassium lithium manganesesilicate), polylithionite (potassium lithium aluminum silicatefluoride), phlogopite (potassium magnesium aluminum silicate hydroxide),preiswerkite (sodium magnesium aluminum silicate hydroxide),siderophyllite (potassium iron aluminum silicate hydroxide), tainiolite(potassium lithium magnesium silicate fluoride), tetra-ferri-annite(potassium iron silicate hydroxide), tetra-ferriphlogopite (potassiummagnesium iron silicate hydroxide), trilithionite (potassium lithiumaluminum silicate fluoride), zinnwaldite (potassium lithium ironaluminum silicate fluoride hydroxide), and mixtures thereof.

Examples of brittle micas include chernykhite (barium vanadium aluminumsilicate hydroxide), margarite (calcium aluminum silicate hydroxide),anadite (barium potassium iron magnesium aluminum silicate hydroxide),bityite (calcium lithium aluminum beryllium silicate hydroxide),clintonite (calcium magnesium aluminum silicate hydroxide),kinoshitalite (barium magnesium aluminum silicate hydroxide), andmixtures thereof.

Examples of interlayer deficient micas include brammallite (sodiumaluminum silicate hydroxide), glauconite (potassium sodium iron aluminummagnesium silicate hydroxide), illite (potassium aluminum silicatehydroxide), wonesite (sodium magnesium aluminum silicate hydroxide), andmixtures thereof.

Useful calcium carbonates include finely ground calcium carbonate.Commercially available forms are available from Harwick Chemical, J. M.Huber Corporation, Georgia Marble, Genstar Stone Products and Omya, Inc.

Useful homogenizing agents include those composed of a mixture of lightcolored resins having a specific gravity of about 1.0 g/cc at 23° C. anda softening point of about 100° C. One particularly suitablehomogenizing agent is available in flake form from Struktol Corporationunder the tradename Struktol® 60 NS.

Alumina trihydrates include finely divided, odorless, crystalline, whitepowders having the chemical formula Al₂O₃.3H₂O. Alumina Trihydrate canbe utilized in the present invention to enhance the green strength ofthe base polymer. Useful alumina trihydrates have an average particlesize ranging from about 0.1 micron to about 5 microns, and morepreferably, from about 0.5 micron to about 2.5 microns.

Alumina trihydrate is commercially available from Franklin IndustrialMaterials, of Dalton, Ga. Notably, alumina trihydrate can also beadvantageously used separately as a flame retardant and smokesuppressant in the EPDM-based roofing membrane composition of thepresent invention.

Other sources of alumina trihydrate are available from J. M. HuberCorporation of Norcross, Ga. under the trademark Micral®. These aluminatrihydrates have a median particle size of about 1.1 microns to about1.5 microns, a specific gravity of about 2.42, an ash content of about64-65 weight percent and a loss on ignition at 1000° F. of about 34.65percent by weight.

Still, an additional useful non-combustible mineral filler suitable forthe present invention is the ore of calcium borate. This filler isavailable in various particle size grades from American Borate Company,Virginia Beach, Va., under the tradename Colemanite® and has thechemical formula Ca₂B₆O₁₁.5H₂O. Colemanite® has a specific gravity ofabout 2.4. Colemanite® may have an average particle size of about 0.1 toabout 5 microns, or from about 0.5 to about 2.5 microns.

Yet another flame-retardant mineral filler which may be particularlysuitable for use in the roofing membrane of the present invention ismagnesium hydroxide. Useful magnesium hydroxides (Mg(OH)₂) includefinely divided, white powders that are extremely effective smokesuppressants as well as a flame-retardant additives.

In one or more embodiments, the EPDM membranes of this invention includeat least about 20%, in other embodiments at least 25%, and in otherembodiments at least about 30% by weight olefinic rubber based on theentire weight of the membrane. In one or more embodiments, the polymericmembranes of this invention include less than 100%, in otherembodiments, less than 50%, and in other embodiments less than about 40%by weight olefinic rubber based on the entire weight of the membrane. Itwill be appreciated that by the term “membrane” as used throughout mayrefer to the entire membrane, in the case of a mono-layer membrane, orto the non-black layer of a multi-layered membrane.

In one or more embodiments, the total content of the fillers used in theproduction of the membranes are less than 300 parts by weight mineralfiller per 100 parts by weight rubber. It will be understood that partsby weight of the component per 100 parts by weight of the rubber (e.g.,elastomeric copolymer) can be referred to as phr. It will also beappreciated that reference to the level or amount of filler in thevulcanizable composition corresponds to the level or amount of filler inthe non-black membrane or non-black layer or the membrane. In otherembodiments less than 220 phr, in other embodiments less than 200 phr,and in other embodiments less than 180 phr filler may be included in themembranes. In one or more embodiments, the vulcanizable compositions(and non-black layers of the membranes) include more than 10 phr, inother embodiments more than 120 phr, and in other embodiments more than200 phr of the filler. Inasmuch as the ingredients of the vulcanizablecomposition of matter are employed to make a non-black membrane (orlayer thereof), the fillers employed are non-black.

In one or more embodiments, at least a threshold amount of the fillerincluded in the vulcanizable composition is a non-black reinforcingfiller. In one or more embodiments, at least 25% by weight, in otherembodiments at least 35% by weight, in other embodiments at least 45% byweight of the filler is a non-black reinforcing filler.

In one or more embodiments, silica is employed as a reinforcingnon-black filler. It will be appreciated that silica filler can providethe entire content of the fillers for the polymeric membrane. In one ormore other embodiments, the filler content can include silica filler andtitanium dioxide. In one or more other embodiments, the total fillercontent can include silica filler, titanium dioxide and talc. In one ormore embodiments, titanium dioxide is considered non-reinforcing filler.

In one or more embodiments, the vulcanizable compositions include atleast 15 phr, in other embodiments at least 20 phr, in other embodimentsat least 20 phr, and in other embodiments at least 25 phr of silicafiller. In one or more embodiments, the vulcanizable compositions mayinclude less than 250 phr, in other embodiments, less than 200 phr, inother embodiments less than 90 phr, and in other embodiments less than80 phr silica filler.

In one or more embodiments, the vulcanizable composition of thisinvention include at least 20 phr, in other embodiments at least 25 phr,in other embodiments at least 35 phr, in other embodiments at least 45phr, and in other embodiments at least 55 phr titanium dioxide. In oneor more embodiments, the vulcanizable composition may include less than90 phr, in other embodiments less than 80 phr, in other embodiments lessthan 75 phr, in other embodiments less than 60 phr, and in otherembodiments at least 65 phr titanium dioxide.

In one or more embodiments, the vulcanizable compositions of thisinvention are devoid of talc. In one or more embodiments, thevulcanizable composition of this invention include at least 5 phr and inother embodiments at least 15 phr talc. In one or more embodiments, thevulcanizable composition may include less than 90 phr and in otherembodiments less than 50 phr talc.

In certain embodiments, the vulcanizable composition is devoid of mica.In other embodiments, the vulcanizable composition of the invention mayinclude at least 6 phr and in other embodiments at least 12 phr mica. Inone or more embodiments, the vulcanizable composition may include lessthan 25 phr and in other embodiments less than 12 phr mica.

In certain embodiments, the vulcanizable composition includes limitedclay. In particular embodiments, the vulcanizable composition is devoidof clay. In one or more embodiments, the vulcanizable compositionincludes less than 15 phr, in other embodiments less than 10 phr, inother embodiments less than 5 phr, and in other embodiments less than 1phr clay.

In certain embodiments, the vulcanizable composition is devoid ofcalcium carbonate. In other embodiments, the vulcanizable compositionsof the invention may include at least 3 phr and in other embodiments atleast 5 phr calcium carbonate. In one or more embodiments thevulcanizable composition may include less than 200 phr and in otherembodiments less than 20 phr calcium carbonate.

In one or more embodiments, the vulcanizable composition includes atleast 0.25 phr NOR-HALS, in other embodiments at least 1.5 phr, in otherembodiments, at least 3 phr, in other embodiments at least 5 phr, and inother embodiments at least 10 phr. In one or more embodiments, thecomposition may include less than 10 phr NOR-HALS, and in otherembodiments less than 5 phr.

In one or more embodiments, the polymeric membranes of this inventioninclude at least 30 phr, in other embodiments at least 40 phr, and inother embodiments at least 50 phr processing oil. In one or moreembodiments, the membrane of the invention may include less than 120phr, and in other embodiments less than 100 phr, and in otherembodiments less than 50 phr processing oil.

The roofing membrane of the present invention can be prepared byconventional means using conventional rubber compounding equipment suchas Brabender, Banbury, Sigma-blade mixer, two-roll mill, or other mixerssuitable for forming viscous, relatively uniform admixtures. Mixingtechniques depend on a variety of factors such as the specific types ofpolymers used, and the fillers, processing oils, waxes and otheringredients used. In one or more embodiments, the ingredients can beadded together in a single shot. In other embodiments, some of theingredients such as fillers, oils, etc. can first be loaded followed bythe polymer. In other embodiments, a more conventional manner can beemployed where the polymer is added first followed by the otheringredients.

Mixing times generally range from about 2 to 6 minutes. In certainembodiments an incremental procedure can be used whereby the basepolymer and part of the fillers are added first with little or noprocess oil, the remaining fillers and process oil are added inadditional increments. In other embodiments, part of the EPDM can beadded on top of the fillers, plasticizers, stabilizers etc. Thisprocedure can be further modified by withholding part of the processoil, and then adding it later. In one or more embodiments, two-stagemixing can be employed.

The sulfur cure package (sulfur/accelerator) can be added near the endof the mixing cycle and at lower temperatures to prevent prematurecrosslinking of the EPDM polymer chains. When utilizing a type B Banburyinternal mixer, the dry or powdery materials such as non-black mineralfillers (i.e., untreated clay, treated clays, talc, mica, and the like)can be added first, followed by the liquid process oil and finally thepolymer (this type of mixing can be referred to as an upside-down mixingtechnique).

The NOR-HALS can be added with the fillers near the beginning of themixing cycle. In one or more embodiments, the NOR-HALS is includedbefore the sulfur cure package is added.

Once mixed, the rubber composition can then be formed into a sheet viacalendering. The compositions of the invention can also be formed intovarious types of articles using other techniques such as extrusion.

The resultant rubbery compositions may be prepared in sheet form in anyknown manner such as by calendering or extrusion. The cured sheets mayalso be cut to the desired dimensions. In one or more embodiments, theresulting admixture can be sheeted to thicknesses ranging from 5 to 200mils, in other embodiments from 35 to 90 mils, by using conventionalsheeting methods, for example, milling, calendering or extrusion. In oneor more embodiments, the non-black admixture is sheeted to the desiredthickness and then bonded to a black sheeting material havingessentially the same characteristics as the non-black sheeting materialof the present invention using conventional processing techniques.Typically, the plies are calendered separately and then laminatedtogether in an uncured state, to be dusted and cured in an autoclave orby other means. The sheeting can be visually inspected and cut to thedesired length and width dimensions after curing.

The calendered sheeting itself should show good, uniform release fromthe upper and lower calender rolls and have a smooth surface appearance(substantially free of bubbles, voids, fish eyes, tear drops, etc.). Itshould also have uniform release from the suction (vacuum) cups at thesplicing table and uniform surface dusting at the dust box.

In one or more embodiments, the rubber formulations disclosed herein forfabricating membranes are employed in the manufacture of bilaminatemembranes wherein the non-black rubber formulations are employed toproduce at least one layer of the laminate membranes. In particularembodiments, the non-black formulations disclosed herein are employed toprepare a first layer, and the second layer can derive from a distinctrubber formulation. In one or more embodiments, the distinct rubberformulation (i.e. the rubber formulation employed to prepare the secondlayer) includes carbon black. Rubber formulations that includeelastomeric copolymer and carbon black are generally known in the art asdisclosed in U.S. Pat. Nos. 6,632,509, 6,615,892, 5,700,538, 5,703,154,5,804,661, 5,854,327, 5,093,206, and 5,468,550 which are incorporatedherein by reference. For example, these black formulations may includeelastomeric olefinic copolymer (i.e. rubber), from about 30 to about 160parts by weight carbon black per 100 parts by weight rubber, 40 to 100parts by weight oil per 100 parts by weight rubber, and otheringredients such as a cure package, antioxidants, cure activators, andthe like. As is known in the art, the carbon black can be replaced orsupplemented with other non-black fillers such as clay and talc.

In one or more embodiments, the laminate membranes of the presentinvention are bilaminates wherein each layer of the membrane accountsfor about 50% of the total thickness of the membrane. For example, a 60mil membrane may include a 30 mil first non-black layer and a 30 milsecond carbon black-filled layer. In other embodiments, the thickness ofthe layers can be different. In fact, it may be advantageous toconstruct a membrane with a non-black layer that is thinner than thecarbon black-filled layer. In one or more embodiments, the thickness ofthe non-black layer to the carbon black-filled layer may be about 1:3 toabout 1:1, in other embodiments from about 1:2.5 to about 1:1.5, or inother embodiments from about 1:2 to about 1:1.8.

The membranes of the present invention can be optionally reinforced witha scrim fabric. In other embodiments, the membranes are devoid of scrimfabric.

The roof sheeting membranes can be evaluated for physical propertiesusing test methods developed for mechanical rubber goods. Typicalproperties include, among others, tensile strength, modulus, ultimateelongation, tear resistance, ozone resistance, water absorption,dimensional stability, burn resistivity, and cured compound hardness. Insome embodiments, the membranes can be tested for weathering resistanceusing the Xenon Arc test as set forth in ASTM D4637 as presently adoptedon the date of filing of this application.

The membranes of this invention can be used as follows. The non-blacklayer can face upward so as to reflect sunlight, and the black layershould face downward toward the building. As the sheet is unrolled overthe roof substructure in a conventional fashion, field seams areprepared by overlapping the edges of a rubber sheet with the edges of anadjacent rubber sheet. The width of the seam can vary depending on therequirements specified by the architect, building contractor, or roofingcontractor and thus, do not constitute a limitation of the presentinvention. Seams can be joined with conventional adhesives such as, forinstance, a butyl-based lap splice adhesive, which is commerciallyavailable from Firestone Building Products Company as SA-1065.Application can be facilitated by spray, brush, swab or other meansknown in the art.

Also, field seams can be formed by using a seam tape and a companionprimer such as QuickSeam™ tape and Quick Prime Plus™ primer, both ofwhich are commercially available from Firestone Building ProductsCompany of Indianapolis, Ind.

Thus it should be evident that the sheeting material and method of thepresent invention are highly effective in covering the roof of abuilding. The invention is particularly suited for use on roofs ofbuildings, but is not necessarily limited thereto. The sheeting materialof the present invention can be used separately with other equipment,methods and the like, such as, for example, for linings for fish ponds,decorative and aquatic gardens, ponds on golf courses, and the like.

In order to demonstrate the practice of the present invention, thefollowing examples have been prepared and tested. The examples shouldnot, however, be viewed as limiting the scope of the invention.Accordingly, for an appreciation of the true scope and breadth of theinvention, reference should be made to the following claims.

The white EPDM membrane developmental work, which used to practice theinvention, started May 2007. The base formula is an experimental whitemembrane formulation (see Table 1 below for details). Mixing, curing andtesting of the formulations were carried out at FSBP lab in Carmel, Ind.

A two-staged mixing process was used. A 300-gram Brabender internalmixer was used to mix the master batch (50 RPM for 3 min at settemperature of 140 C, drop temperature is 170 C). A 13″×6″ two-roll openmill is used to mix the final batch (roll temperature 88 C, thecuratives were mixed into MB—stock passes at 25 times between two rollsof the mill).

Uncured compounds were tested in a MDR2000 for their processingproperties. Compounds were cured with a hot press for 45 min at 160 C.Cured samples were die-cut and tested according to ASTM D4637 and someof the results are provided in Table 2.

TABLE 1 Formulations Compound ID D2955 D2976 D2977 Ingredient 239230EPDM Royalene 512 100.00 100.00 100.00 Silica RS-150D 51.20 51.20 51.20TiO2 CR800 58.20 58.20 58.20 Mistron Vapor Talc 40.60 40.60 40.60 WhiteOil FHR Ultra 1199 59.42 59.42 59.42 Carbowax 3350 1.99 1.99 1.99 WaxStruktle PE H100 5.01 5.01 5.01 Zinc Oxide Kadox 911 5.01 5.01 5.01Stearic Acid 2.5 2.5 2.5 NOR HALS Tinuvin 0 1.5 3 XT833 Master BatchTotal 323.9 325.4 326.9 MB 323.9 325.4 326.9 Sulfur 0.97 0.97 0.97 ZincDBDC 1.46 1.46 1.46 MBTS 0.30 0.30 0.30 Stearic Acid 0.75 0.75 0.75Final Batch Total 327.4 328.9 330.4

TABLE 2 Selected properties of white EPDM compounds ASTM Compound IDD2975 D2976 D2977 D4637 Compounds mixed at Carmel lab Property MinimumMooney 29.4 28.2 27.5 NA Viscosity, MU Scorch time t5, minute 18.6 20.220.9 NA Scorch time t35, minute 24.7 27.4 28.8 NA Dumbbell Tensile 73 F.(45 min/320 F. cure) 100% Modulus, psi 216 195 199 NA Tensile Strength,psi 1536 1337 1352 1305 min Elongation at break, % 722 737 730  300 minDumbbell Tensile 73 F. (5 hrs/320 F. cure) 100% Modulus, psi 259 250 254NA Tensile Strength, psi 1793 1777 1766 NA Elongation at break, % 713710 702 NA Die C tear resistance 73 F. Max load 73 F., lb/in (45 160 155157  125 min min/320 F. cure) Max load 73 F., lb/in (5 149 150 150 NAhrs/320 F. cure

Additional samples of uncured white EPDM compounds were made and testingperformed on those samples as well. These additional samples are setforth in Table 3,

TABLE 3 Additional Formulations and Selected Properties of EPDM CompundsD3113 Compound No (control) D3114 D3115 D3116 D3117 D3118 FormulationR512, ENB = 3.9%, ML1 + 100.0 100.0 100.0 100.0 4 = 53, 125 C. R4569,ENB/DCPD = 2.4/0.4%, 100.0 100.0 ML1 + 4 = 60, 125 C. Rubbersill 15051.20 51.20 51.20 51.20 51.20 51.20 TiO2/CR800, Tronox LLC, d~3.8 58.2058.20 58.20 58.20 58.20 58.20 Mistron Vapor Talc, d~2.8 40.60 40.6040.60 40.60 40.60 40.60 FHR Ultra 1199 (White Oil) 59.42 59.42 59.4259.42 59.42 59.42 Deolink MX silane 2.00 2.00 2.00 2.00 2.00 2.00Carbowax 3350 1.99 1.99 1.99 1.99 1.99 1.99 Afflux PE 12 5.01 5.01 5.015.01 5.01 5.01 Kadox 911 (white ZnO), d = 5.6 5.01 5.01 5.01 5.01 5.015.01 Vanox ZMTI 1.50 Irganox 1076 or Anox PP18, 1.50 1.50 1.50 Tm =50-55 C. Tinuvin XT833, Tm = 63-75 C. 1.50 1.50 1.50 Stearic Acid 2.502.50 2.50 2.50 2.50 2.50 Master Batch Total 325.93 325.93 328.93 328.93327.43 328.93 MB 325.93 325.93 328.93 328.93 327.43 328.93 Sulfur 1.501.50 1.50 1.50 1.50 1.50 Zinc DBDC (Butazate) 1.46 1.46 1.46 1.46 1.461.46 MBTS 0.30 0.30 0.30 0.30 0.30 0.30 Stearic Acid 0.75 0.75 0.75 0.750.75 0.75 Fnial Batch Total 329.94 329.94 332.94 332.94 331.44 332.94 3″× 6″ cured membrane properties initial weight 10.6292 9.7968 10.067310.5400 10.6258 10.9453 weight at 24 months 10.4135 9.5992 9.858110.3741 10.4395 10.7816 Weight loss after 24 months 0.2157 0.1976 0.20920.1659 0.1863 0.1637 weathering loss less than control (D3113- 0.00%8.39% 3.01% 23.09% 13.63% 24.11% Dxxx)/D3113 × 100%

In these tests shown in Table 3, 6 specimens were subjected to exposuretesting at New River, Ariz. in accordance with ASTM G90, Spray Cycle 1(EMMAQUA, day spray with night time wetting). EMMAQUA is an acceleratedweathering test using 7 to 8 mirrors to concentrate solar radiation onthe testing samples. The specimens were mounted backed on paper facedplywood, with the uncoded side facing the sun. Before original weightwas taken, ½ inch was cut from the bottom of each specimen to use as acontrol. The protective wrap was removed.

Exposure was tested for 24 months. Specimens were inspected and testedevery 3 months, wherein they were not subject to exposure for a periodof up to 7 days during this time. At 24 months, the weight loss of thespecimens due to weathering was recorded. It will be appreciated thatthe specimens that included the NOR-HALS UV light stabilizer had a lowerweight loss than the control specimen which had no such lightstabilizer. In fact, the specimens that included both the NOR-HALS UVlight stabilizer and the Irganox material, (a typical antioxidant usedin rubber products), performed the best in the study.

Furthermore, it is well known that white (or non-black) roofingmembranes (both EPDM and TPO) deteriorate during their service on roofs.The typical failure mode is chalking due to polymer degradation. Thetest results clearly show that the specimens in Table 3 with theNOR-HALS stabilizer reduces chalking after 2 years of extensiveweathering.

Various modifications and alterations that do not depart from the scopeand spirit of this invention will become apparent to those skilled inthe art. This invention is not to be duly limited to the illustrativeembodiments set forth herein.

What is claimed is:
 1. A bilaminate roofing membrane comprising: (i) afirst layer including a sulfur-cured EPDM rubber, where the first layerincludes silica and a UV light stabilizer dispersed within the EPDMrubber, where the UV light stabilizer is a NOR-HALS compound defined bythe formula

wherein R* is C₁-C₂₀alkyl, OH-substituted C₁-C₂₀alkyl, optionally C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, C₇-C₉phenylalkyl or O- orS-interrupted C₂-C₂₀alkyl; (ii) a second layer including a sulfur-curedEPDM rubber, where the second layer includes carbon black dispersedwithin the EPDM rubber, where the second layer is substantially devoidof the NOR-HALS compound; and (iii) optionally a scrim disposed betweensaid first and second layers.
 2. The bilaminate roofing membrane ofclaim 1, where R* is C₁-C₁₂alkyl, benzyl, or C₅-C₈ cycloalkyl.
 3. Thebilaminate roofing membrane of claim 2, where R* is C₆-C₁₀alkyl orcyclohexyl.
 4. The bilaminate roofing membrane of claim 1, where saidfirst layer further includes titanium dioxide.
 5. The bilaminate roofingmembrane of claim 1, where said first layer further includes avulcanizing accelerator or residue thereof.
 6. The bilaminate roofingmembrane of claim 5, where the vulcanizing accelerator is selected fromthe group consisting of thioureas, thiuram monosulfides and disulfides,benzothiazole sulfonamides, thiazole accelerators, and dithiocarbamates.7. The bilaminate roofing membrane of claim 4, where said first layerfurther includes mica.
 8. A roofing membrane comprising at least onenon-black layer prepared from a vulcanizable composition of matterincluding: an EPDM rubber; a non-black filler including silica; a UVlight stabilizer selected from the group consisting of NOR-HALS of theformula

wherein R* is C₁-C₂₀alkyl, OH-substituted C₁-C₂₀alkyl, optionally C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, C₇-C₉phenylalkyl or O- orS-interrupted C₂-C₂₀alkyl; wherein the vulcanizable composition ofmatter contains from about 0.01 to about 10 wt. % of the UV lightstabilizer; and a cure package.
 9. The roofing membrane of claim 8,where the membrane includes first and second layers laminated to eachother, optionally with a scrim disposed there between, where the firstlayer is the at least one non-black layer and the second layer is ablack layer.
 10. The roofing membrane of claim 9, where the black layeris prepared from a vulcanizable composition including EPDM rubber,carbon black, and a cure package.
 11. The roofing membrane of claim 10,where the vulcanizable composition used to prepare the black layer issubstantially devoid of NOR-HALS.
 12. The roofing membrane of claim 8,where the vulcanizable composition further includes a vulcanizationaccelerator selected from the group consisting of thioureas, thiurammonosulfides and disulfides, benzothiazole sulfonamides, thiazoleaccelerators, and dithiocarbamates.
 13. The roofing membrane of claim12, where the EPDM rubber forms a rubber component, and where the rubbercomponent consists essentially of the EPDM rubber.
 14. The roofingmembrane of claim 1, wherein the roofing membrane provides increasedweathering resistance as tested according to the Xenon Arc test of ASTMD4637.
 15. A method for the production of a roofing membrane, the methodcomprising: (i) mixing an EPDM rubber, silica, a curative, and a UVstabilizer selected from the group consisting of NOR-HALS of the formula

wherein R* is C₁-C₂₀alkyl, OH-substituted C₁-C₂₀alkyl, optionally C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, C₇-C₉phenylalkyl or O- orS-interrupted C₂-C₂₀alkyl, wherein the vulcanizable composition containsfrom about 0.01 to about 10 wt. % of the UV light stabilizer; (ii)calendering the vulcanizable composition into one or more layers to forma sheet; and (iii) curing the sheet such that the EPDM rubber hasimproved resistance to UV light as compared to an EPDM membrane madecomparably, but without the same UV stabilizer.
 16. The method of claim15, where the curative is sulfur, and where the vulcanizable compositionfurther includes a vulcanization accelerator.
 17. The method of claim16, where the vulcanization accelerator is selected from the groupconsisting of thioureas, thiuram monosulfides and disulfides,benzothiazole sulfonamides, thiazole accelerators, and dithiocarbamates.